Readily accessible and easily modifiable Ru-based catalysts for efficient and Z-selective ring-opening metathesis polymerization and ring-opening/cross-metathesis.

Rationally designed Ru-based catalysts for efficient Z-selective olefin metathesis are featured. The new complexes contain a dithiolate ligand and can be accessed in a single step from commercially available precursors in 68-82% yield. High efficiency and exceptional Z selectivity (93:7 to >98:2 Z:E) were achieved in ring-opening metathesis polymerization (ROMP) and ring-opening/cross-metathesis (ROCM) processes; the transformations typically proceed at 22 °C and are operationally simple to perform. Complete conversion was observed with catalyst loadings as low as 0.002 mol %, and turnover numbers of up to 43,000 were achieved without rigorous substrate purification or deoxygenation protocols. X-ray data and density functional theory computations provide support for key design features and shed light on mechanistic attributes.